CN117282121A - Recovery method and device for lithium battery waste oil film - Google Patents
Recovery method and device for lithium battery waste oil film Download PDFInfo
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- CN117282121A CN117282121A CN202310437363.0A CN202310437363A CN117282121A CN 117282121 A CN117282121 A CN 117282121A CN 202310437363 A CN202310437363 A CN 202310437363A CN 117282121 A CN117282121 A CN 117282121A
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- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 248
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 124
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 116
- 239000000284 extract Substances 0.000 claims abstract description 88
- 239000012530 fluid Substances 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims description 46
- 239000012634 fragment Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000012454 non-polar solvent Substances 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 127
- 239000007789 gas Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000194 supercritical-fluid extraction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- -1 methane alkane Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The application provides a recovery method of a lithium battery waste oil film, which comprises the following steps: treating the waste oil film into an extract; heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid; contacting a supercritical carbon dioxide fluid with the extract to selectively dissolve an extract of the extract to be extracted that is soluble in the carbon dioxide fluid; and reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide. The application obtains the dissolved extract and the carbon dioxide of separation white oil and plastics, and then utilizes current waste oil regeneration equipment technique to obtain the regeneration white oil, and the terminal product does not belong to the danger useless, accords with environmental protection regulation policy, realizes danger useless resource recycle, accomplishes resource utilization maximize.
Description
Technical Field
The application relates to the field of waste oil film treatment, in particular to a recovery method of a lithium battery waste oil film. The application also relates to a recovery device of the lithium battery waste oil film.
Background
The production process flow for producing the lithium ion battery diaphragm by the wet method generally adopts a synchronous biaxial stretching process, and the process flow approximately comprises the following steps: proportioning, extrusion plasticizing, cooling of cast sheets, biaxial stretching, extraction drying, rolling inspection, slitting and packaging and the like. The waste white oil generated in the production process of the lithium battery diaphragm belongs to dangerous waste. In the process of preparing the wet diaphragm, waste oil films are generated due to trimming and the like, and PE or PP plastics belong to olefins and white oil belongs to alkanes). There is no good recycling mode for this waste oil film, and the existing disposal modes include:
1. incineration or burial. The waste is treated by dangerous waste company, the combustion heat value is used for generating electricity or heating, and the like, and the value utilization rate is very low.
2. Regenerating the particles. A small part of oil is separated by crushing, extrusion, high-speed centrifugation and the like, and the oil is reused by a multi-stage purification device or a recycling process such as reduced pressure distillation and the like. And then the residual oil film is used for producing regenerated particles (oil content is more than 50 percent, and the oil is still dangerous waste, and the disposal mode is not compliant).
3. And (5) a cracking process. The lysis treatment includes two ways: producing PE wax, namely producing PE wax by incomplete cracking products and simultaneously producing alkane with methane as a main component; the plastic oil refining uses the completely cracked product as the main component and is composed of methane alkane, gasoline and diesel oil, etc.
4. Separation techniques. Common separation techniques include extraction, centrifugation, ultrasonic waves and the like, but the recovery efficiency is poor by adopting common centrifugation, ultrasonic waves and the like, and the technology is not feasible. White oil (alkane) belongs to a nonpolar solvent, and according to a similar compatibility principle, the nonpolar solvent must be selected for extraction separation, and common organic solvents which can be selected include dichloromethane, carbon tetrachloride, heptane and the like.
The prior art has the defects that:
1. the existing crushing extrusion, high-speed centrifugation and other modes can not realize the separation of plastic and white oil, the separation effect is extremely poor, the oil content of regenerated particles produced by using waste oil films is more than 50%, the waste is still dangerous according to the dangerous waste identification method standard, and the waste is the behavior violating environmental protection regulations.
2. The existing waste oil regeneration process (multi-stage purification, reduced pressure distillation and the like) mainly aims at liquid waste mineral oil, and can not directly process an oily waste oil film, and the existing process has application limitation.
3. Most procedures of enterprises for preparing PE wax through pyrolysis are not compliant, and the PE wax obtained by the scheme has low product rate and is not economical; the adoption of the complete cracking is a large petrochemical enterprise, no technological package aiming at the separation of the substances is adopted, the small project is very difficult, and the application of the terminal product is very limited.
4. The extraction process can realize the separation of the two, methylene dichloride (low boiling point and easy volatilization) is selected as an extractant in the existing wet method diaphragm preparation, and then the methylene dichloride is recycled by utilizing a gas recovery device and a liquid recovery device. If the mode of selecting methylene dichloride or other organic solvents is simulated, various problems of high production process danger, high recovery cost, environmental pollution and the like exist.
Disclosure of Invention
The utility model aims to overcome the defects of the prior art that waste oil films are recovered, the difficulty is high, the cost is high, or waste gas and waste are generated, and the environmental protection requirement cannot be met, and provides a recovery method of lithium battery waste oil films. The application also relates to a recovery device of the lithium battery waste oil film.
The application provides a recovery method of a lithium battery waste oil film, which comprises the following steps:
treating the waste oil film into an extract;
heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid;
contacting a supercritical carbon dioxide fluid with the extract to selectively dissolve an extract of the extract to be extracted that is soluble in the carbon dioxide fluid;
and reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide.
Optionally, the processing into the extract comprises:
and crushing the waste oil film to generate oil film fragments.
Optionally, a nonpolar solvent is added to the carbon dioxide gas as an entrainer.
Optionally, said contacting supercritical carbon dioxide fluid with said oil film fragments comprises:
the boosted supercritical carbon dioxide fluid enters a carbon dioxide extraction reaction kettle through a pressure reducing valve to contact with the oil film fragments.
Optionally, the obtaining the extract and carbon dioxide gas includes:
and (3) introducing the supercritical carbon dioxide fluid containing the extract into a separation reaction kettle through a metering valve, and reducing the pressure to separate out the extract and carbon dioxide.
Optionally, after the extract and the carbon dioxide are obtained, the method further includes:
the extract and the carbon dioxide enter a cold trap separator through a back pressure valve;
and taking out the extract, and recovering the carbon dioxide to enter the next round of extraction.
The application also provides a recovery unit of lithium cell waste oil film, include:
a particle module for treating the waste oil film into an extract;
the fluid module is used for heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid;
an extraction module for contacting supercritical carbon dioxide fluid with the extract to selectively dissolve the extract of the extract to be extracted which can be dissolved in the carbon dioxide fluid;
and the separation module is used for reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract and obtaining the extract and the carbon dioxide.
Optionally, the extraction module includes:
and the injection unit is used for enabling the boosted supercritical carbon dioxide fluid to enter the carbon dioxide extraction reaction kettle through the pressure reducing valve to contact with the oil film fragments.
Optionally, the separation module includes:
the pressure reducing unit is used for enabling the supercritical carbon dioxide fluid containing the extract to enter the separation reaction kettle through the metering valve, and reducing the pressure to separate out the extract and the carbon dioxide.
Optionally, the separation module further includes:
the transfer unit is used for enabling the extract and the carbon dioxide to enter the cold trap separator through the back pressure valve;
and the recovery unit is used for taking out the extract and recovering the carbon dioxide to enter the next round of extraction.
The application has the advantages and beneficial effects that:
the application provides a recovery method of a lithium battery waste oil film, which comprises the following steps: treating the waste oil film into an extract; heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid; contacting a supercritical carbon dioxide fluid with the extract to selectively dissolve an extract of the extract to be extracted that is soluble in the carbon dioxide fluid; and reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide. The application obtains the dissolved extract and the carbon dioxide of separation white oil and plastics, and then utilizes current waste oil regeneration equipment technique to obtain the regeneration white oil, and the terminal product does not belong to the danger useless, accords with environmental protection regulation policy, realizes danger useless resource recycle, accomplishes resource utilization maximize.
Drawings
Fig. 1 is a schematic diagram of a recovery flow of a lithium battery waste oil film in the present application.
Fig. 2 is a schematic diagram of a recovery process of a lithium battery waste oil film in the present application.
Fig. 3 is a schematic diagram of the recovery extraction process of the lithium battery waste oil film in the present application.
Fig. 4 is a schematic diagram of the recovery extraction result of the lithium battery waste oil film in the present application.
Fig. 5 is a schematic structural diagram of a recovery system of lithium battery waste oil film in the present application.
Detailed Description
The present application is further described in conjunction with the drawings and detailed embodiments so that those skilled in the art may better understand the present application and practice it.
The following are examples of specific implementation provided for the purpose of illustrating the technical solutions to be protected in this application in detail, but this application may also be implemented in other ways than described herein, and one skilled in the art may implement this application by using different technical means under the guidance of the conception of this application, so this application is not limited by the following specific embodiments.
The application provides a recovery method of a lithium battery waste oil film, which comprises the following steps: treating the waste oil film into an extract; heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid; contacting a supercritical carbon dioxide fluid with the extract to selectively dissolve an extract of the extract to be extracted that is soluble in the carbon dioxide fluid; and reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide. The application obtains the dissolved extract and the carbon dioxide of separation white oil and plastics, and then utilizes current waste oil regeneration equipment technique to obtain the regeneration white oil, and the terminal product does not belong to the danger useless, accords with environmental protection regulation policy, realizes danger useless resource recycle, accomplishes resource utilization maximize.
As shown in fig. 1 and 2, the method for recovering the lithium battery waste oil film comprises the following steps:
s101, treating the waste oil film into an extract.
In step S101, the production process of the regenerated particles is roughly divided into: crushing process, drying process, granulating process and granulating process.
After the waste oil film is crushed, melt extrusion is performed by heating, and then pelletization is performed, and finally regenerated particles are obtained as an extract to be extracted. The extract to be extracted comprises an oil film and white oil contained in the oil film.
In a preferred embodiment, the waste oil film is crushed to directly form the extract.
The regenerated particles are produced by treating the deoiling membrane after extraction and separation or oil film treatment before extraction.
Specifically, pretreatment of waste oil films includes two modes:
the mechanical crushing treatment is directly carried out, the diameter of crushed fragments is as small as possible, the particle size is preferably 250-830 mu m, and the crushed oil film is used as an extract to be extracted.
Further, the crushed oil film may be melt extruded to form granule with particle size of 20-60 mesh.
S102, heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid.
In step S102, the supercritical fluid is contacted with the substance to be separated, and white oil is extracted therefrom.
When the substance is in a supercritical state, the substance becomes a single-phase state with the property between that of liquid and gas, has the density similar to that of the liquid, has the viscosity higher than that of the gas but obviously lower than that of the liquid, and has the diffusion coefficient 10-100 times that of the liquid, so that the substance has better permeability and stronger dissolving capacity to the material, and can extract certain components in the material.
The density, polarity and dielectric constant of supercritical fluid increase with the pressure of closed system, and the components with different polarities can be extracted step by using the pressure increase of preset program.
Of course, the extracts obtained corresponding to the pressure ranges cannot be single, but the mixed components with the optimal proportion can be obtained by controlling conditions such as temperature and pressure, then the supercritical fluid is changed into common gas or liquid by means of decompression and temperature rising and falling methods, and the extracts are automatically and completely separated out, so that the purposes of separation and purification are achieved, and the extraction and separation processes are integrated.
In the application, carbon dioxide (CO 2) is selected as an extractant (supercritical CO2 belongs to a nonpolar solvent), and the waste oil film is circularly extracted, so that the low-cost and pollution-free operation is realized. And the method is considered to be connected with the upstream and downstream existing technologies, so that economical and continuous production is realized.
Carbon dioxide is used as the extractant, while it is contemplated that certain proportions of non-polar solvents, such as non-polar solvents including carbon tetrachloride, trichloroethane, may be added as entrainers.
Meanwhile, the most economical and efficient parameter scheme is finally obtained by adjusting the pressure and the temperature and the influence on the extraction efficiency after the entrainer is added. The temperature, pressure and entrainer metering can be set and proportioned to obtain optimal effect through experiments.
The supercritical extraction equipment has different separation and extraction efficiencies at different temperatures and pressures, and the application is used for researching the waste oil films with different particle sizes and different mixing ratios and the separation efficiencies of the supercritical extraction equipment at different pressures and different temperatures. And then mixing and re-granulating the separated waste oil film and the deoiling diaphragm in different proportions to obtain regenerated particles meeting the product quality requirement.
S103, contacting supercritical carbon dioxide fluid with the to-be-extracted matters, and selectively dissolving the extracts which can be dissolved in the carbon dioxide fluid in the to-be-extracted matters.
In step S103, a mating process is selected according to physicochemical properties of white oil obtained by extraction and separation, and a multi-stage filtration device may be selected, and reduced pressure distillation, hydrofining and other manners may be adopted to obtain reclaimed oil. The white oil obtained after separation is regenerated mainly by the technology.
The carbon dioxide gas is heated and pressurized to form a liquid, and further becomes a supercritical carbon dioxide fluid, and the supercritical carbon dioxide fluid can be generated by setting different temperatures and/or air pressures, and is not limited herein.
Preferably, the pressure is raised to 30-40MPa by a booster pump, and the temperature is regulated to 32-70 ℃ so as to become supercritical carbon dioxide fluid.
Preferably, the temperature is set to 65 ℃ and the pressure is set to 35MPa, and the CO2 flow is controlled to 95L/h.
Preferably, an isothermal pressure-variable method, i.e. a constant temperature, can be used, in which the temperature of the pressure is adjusted to increase and the dissolution capacity is reduced, in which case the temperature just exceeding the supercritical pressure is selected.
Carbon dioxide fluid is taken as a solvent to enter from the bottom of the extraction full-automatic reaction kettle and fully contacts with oil film fragments, so that white oil in the oil film fragments is selectively dissolved, a deoiling diaphragm and white oil mixed liquid dissolved in supercritical CO2 fluid are obtained, and meanwhile, the oil film fragments become fragments of plastic materials.
S104, reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide.
The high-pressure carbon dioxide fluid containing the extract is depressurized by a throttle valve to be lower than the supercritical pressure of the carbon dioxide and enters a full-automatic separation reaction kettle (also called a full-automatic desorption kettle).
The pressure of the separation kettle is reduced, so that the solubility of carbon dioxide is rapidly reduced to separate white oil, the white oil is automatically separated into two parts, namely white oil and carbon dioxide gas, the white oil and the carbon dioxide gas are periodically discharged from the bottom of the separation kettle, and the carbon dioxide gas is recycled through heating and pressurizing to form carbon dioxide liquid for recycling.
By adopting the cyclic extraction separation process, the white oil in the waste oil film can be completely extracted with the increase of time, and the separation effect close to 100% is finally realized.
As shown in fig. 5, the supercritical carbon dioxide plant operating system workflow:
gaseous or liquid CO2 flows from the storage tank 201, the filter 208, the cold box and storage tank 207, the heater, the oil-free pollution-free booster pump (boost), the pressure reducing valve (flow pressure and adjustment), the full-automatic CO2 extraction reaction kettle 206 (extraction sample), the precise metering valve (flow adjustment), the full-automatic separation reaction kettle 203 (extraction product and CO2 separation), the back pressure valve (flow pressure and adjustment), the cold trap separator, the gas flowmeter, the digital display type accumulation flowmeter, and the CO2 recovery tank 202. The separated product, including white oil and plastic, is fed into an oil reservoir 204 and a storage space 205, respectively.
The method for testing the oil content of the oil-containing waste oil film comprises the following steps:
the application test was performed with a 2L format of small test equipment.
1000g of oil-containing waste oil film sample is weighed, and is circularly extracted by a supercritical extraction device until white oil is not separated out from a separation kettle, and the separated white oil is weighed to obtain Mg with the oil content of M/1000 x 100 percent. This value can be verified by comparison with data obtained by complete extraction with an organic solvent such as methylene chloride, heptane, etc.
For example:
(1) 700g of an oil film sample of the oil-containing waste (white oil content: 65%) was weighed, and the oil film was broken into pieces of 0.5-1cm and put into an extraction tank.
(2) The carbon dioxide gas is heated and pressurized into liquid, the pressure is raised to 35MPa by a pressurizing pump, and the temperature is heated to 65 ℃ at the same time, so that the supercritical carbon dioxide fluid is formed.
(3) Carbon dioxide fluid is taken as a solvent to enter from the bottom of the extraction full-automatic reaction kettle and fully contacts with oil film fragments, so that white oil in the oil film fragments is selectively dissolved.
(4) The high-pressure carbon dioxide fluid containing the dissolved extract is depressurized by a throttle valve to be lower than the supercritical pressure of the carbon dioxide and enters a full-automatic separation reaction kettle (a separation kettle for short).
(5) The temperature of the carbon dioxide separation kettle is 65 ℃ and the pressure is 5.6MPa, white oil is separated out due to the rapid reduction of the solubility of carbon dioxide, the white oil is automatically separated into two parts of white oil and carbon dioxide gas, the white oil is a process product, the white oil is periodically discharged from the bottom of the separation kettle, the carbon dioxide gas is recycled, and the carbon dioxide liquid is recycled through heating and pressurizing.
(6) The test adopts continuous dynamic circulation extraction, the CO2 flow is set to be 95L/h, and the recovery can be realized near 100% after the dynamic extraction is carried out for 3 hours. (extraction = weight separated white oil/white oil content 100%).
As shown in FIG. 4, the separated white oil discharged from the separation tank every half an hour was weighed, and it was verified by test that 225g of oil was discharged at half an hour, 350g of oil was discharged at 1.5 hours, 390 g of oil was discharged at 2 hours, 425g of oil was discharged at 2.5 hours, 450g of oil was discharged at 3 hours, and 455g of oil was discharged at 3 hours. The data of the white oil content are circularly extracted by a supercritical extraction device until the white oil is not separated out from a separation kettle, and the separated white oil is weighed to obtain Mg and the oil content
＝M/1000*100％。
It was found that 76.92% of the oil could be separated in 1 hour.
The following provides the experimental results under different experimental conditions of the present application:
the first group of 2-3mm oil film fragments (oil content 60%) weighed 1869g; the method comprises the steps of carrying out a first treatment on the surface of the After 12 hours of static soaking, dynamic extraction was started.
Initial parameters: extracting kettle pressure is 35MPa, temperature is 55 ℃, and flow is 95L/h; the pressure of the separation kettle is 5.6MPa and the temperature is 55 ℃.
The second group of 2-3mm oil film fragments (oil content 60%) are weighed 950g and put into an extraction kettle, and then dynamic extraction (without soaking) is directly carried out;
initial parameters: extracting kettle pressure is 35MPa, temperature is 45 ℃, and flow is 95L/h; the pressure of the separation kettle is 5.6MPa and the temperature is 45 ℃. After 1 hour, the extraction effect was found to be poor, and the temperature was adjusted to 65 ℃. The final test effect is not ideal.
And crushing an oil film with the oil content of 65%, weighing 950g, and directly performing dynamic extraction after the oil film with the oil content of 20cm x 20cm is crushed in the third group.
Initial parameters: extracting kettle pressure is 35MPa, temperature is 55 ℃, and flow is 95L/h; the pressure of the separation kettle is 5.6MPa and the temperature is 55 ℃.
And the fourth group firstly breaks oil film with 65% oil content, the breaking size is 3-5cm, and after weighing 795g, the oil film is put into an extraction kettle, the dynamic extraction is directly carried out.
Initial parameters: extracting kettle pressure is 35MPa, temperature is 55 ℃, and flow is 95L/h; the pressure of the separation kettle is 5.6MPa and the temperature is 55 ℃.
And the fifth group firstly breaks oil film with 65% oil content, the breaking size is 0.5-1cm, and the dynamic extraction is directly carried out after 700g of oil film is weighed into an extraction kettle.
Initial parameters: extracting kettle pressure is 35MPa, temperature is 55 ℃, and flow is 95L/h; the pressure of the separation kettle is 5.6MPa and the temperature is 55 ℃.
According to the experiment, the smaller the crushing size is, the faster the extraction speed is, the better the effect is, and meanwhile, the application can completely extract the waste oil film by 100.00%, and meanwhile, the hazardous waste is not caused.
Claims (10)
1. The recovery method of the lithium battery waste oil film is characterized by comprising the following steps:
treating the waste oil film into an extract;
heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid;
contacting a supercritical carbon dioxide fluid with the extract to selectively dissolve an extract of the extract to be extracted that is soluble in the carbon dioxide fluid;
and reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract, and obtaining the extract and the carbon dioxide.
2. The method for recovering a lithium battery waste oil film according to claim 1, wherein the treating into an extract comprises:
and crushing the waste oil film to generate oil film fragments.
3. The method for recovering waste oil film of lithium battery according to claim 1, wherein a nonpolar solvent is added to the carbon dioxide gas as an entrainer.
4. The method of recovering a lithium battery waste oil film according to claim 2, wherein said contacting the supercritical carbon dioxide fluid with the oil film fragments comprises:
the boosted supercritical carbon dioxide fluid enters a carbon dioxide extraction reaction kettle through a pressure reducing valve to contact with the oil film fragments.
5. The method for recovering a lithium battery waste oil film according to claim 1, wherein the obtaining the extract and carbon dioxide gas comprises:
and (3) introducing the supercritical carbon dioxide fluid containing the extract into a separation reaction kettle through a metering valve, and reducing the pressure to separate out the extract and carbon dioxide.
6. The method for recovering a lithium battery waste oil film according to claim 1 to 5, further comprising, after the extraction and the carbon dioxide are obtained:
the extract and the carbon dioxide enter a cold trap separator through a back pressure valve;
and taking out the extract, and recovering the carbon dioxide to enter the next round of extraction.
7. The utility model provides a recovery unit of lithium cell waste oil film which characterized in that includes:
a particle module for treating the waste oil film into an extract;
the fluid module is used for heating and pressurizing carbon dioxide to generate supercritical carbon dioxide fluid;
an extraction module for contacting supercritical carbon dioxide fluid with the extract to selectively dissolve the extract of the extract to be extracted which can be dissolved in the carbon dioxide fluid;
and the separation module is used for reducing the supercritical carbon dioxide fluid containing the extract to be lower than the supercritical pressure of carbon dioxide, separating out the extract and obtaining the extract and the carbon dioxide.
8. The device for recovering waste oil film of lithium battery according to claim 7, wherein the extraction module comprises:
and the injection unit is used for enabling the boosted supercritical carbon dioxide fluid to enter the carbon dioxide extraction reaction kettle through the pressure reducing valve to contact with the oil film fragments.
9. The apparatus for recovering waste oil film of lithium battery according to claim 7, wherein the separation module comprises:
the pressure reducing unit is used for enabling the supercritical carbon dioxide fluid containing the extract to enter the separation reaction kettle through the metering valve, and reducing the pressure to separate out the extract and the carbon dioxide.
10. The recovery device for lithium battery waste oil film according to claims 7 to 9, wherein the separation module further comprises:
the transfer unit is used for enabling the extract and the carbon dioxide to enter the cold trap separator through the back pressure valve;
and the recovery unit is used for taking out the extract and recovering the carbon dioxide to enter the next round of extraction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310292050 | 2023-03-23 | ||
| CN2023102920500 | 2023-03-23 |
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| Publication Number | Publication Date |
|---|---|
| CN117282121A true CN117282121A (en) | 2023-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310437363.0A Pending CN117282121A (en) | 2023-03-23 | 2023-04-23 | Recovery method and device for lithium battery waste oil film |
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| Country | Link |
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| CN (1) | CN117282121A (en) |
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